CN113121792B - UV-cured fluorine-modified waterborne epoxy resin and preparation method thereof - Google Patents
UV-cured fluorine-modified waterborne epoxy resin and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/145—Compounds containing one epoxy group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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Abstract
The invention relates to the field of ultraviolet light curing water-based paint, in particular to a preparation method of UV curing fluorine modified water-based epoxy resin, which comprises the following steps: synthesizing fluorine-containing prepolymer: adding 30-32 parts by weight of epoxy resin, 0.1-0.2 part by weight of polymerization inhibitor, 0.5-0.8 part by weight of catalyst and 0.1-0.2 part by weight of antioxidant into a synthesis device, heating to 95-100 ℃, dropwise adding 10-12 parts by weight of acrylic acid and 30-60 parts by weight of fluorine-containing carboxylic acid, heating to 110 ℃ and reacting for 3 hours until the acid value AV is less than 5, thus obtaining fluorine-containing prepolymer; synthesizing fluorine modified water-based epoxy resin: adding 35-38 parts by weight of fluorine-containing prepolymer into reaction equipment, stirring at 80+/-2 ℃, adding 5-10 parts by weight of anhydride, stirring at 95-100 ℃ for 3h, adding 5-8 parts by weight of triethylamine, stirring for 30min, adding 40-60 parts by weight of deionized water, and stirring at 50 ℃ for 1h to obtain fluorine-modified waterborne epoxy resin. The invention provides the UV-cured fluorine modified waterborne epoxy resin with strong water resistance, good weather resistance and high mechanical strength.
Description
Technical Field
The invention relates to the field of ultraviolet light curing water-based paint, in particular to a UV curing fluorine modified water-based epoxy resin and a preparation method thereof.
Background
The photo-curing paint is also called photosensitive paint, which uses ultraviolet light as paint curing energy source, and can be quickly cured into film on flammable substrates such as paper, plastics, leather, wood and the like without heating. The photo-curing coating has the advantages of short curing time (a fraction of a second to a few minutes), low curing temperature, low volatile components and the like.
Today, the society has increasingly high environment-friendly call, and the traditional UV epoxy resin needs a large amount of reactive diluents and organic solvents in the construction process, so that the environment is seriously polluted when the UV epoxy resin is used, the UV epoxy resin is unsafe, and the UV epoxy resin is greatly harmful to human bodies. Therefore, research and development of the water-based UV epoxy resin become one of the directions of urgent development, and the water-based UV epoxy resin not only inherits the energy conservation and high efficiency of the traditional epoxy, but also can avoid the harm of the reactive diluent and the organic solvent to human bodies. Meanwhile, after the common aqueous UV epoxy resin is cured, the water resistance and weather resistance are poor, and the mechanical strength is insufficient. This also limits the application of ordinary waterborne UV epoxy to photocurable coatings and does not meet market demand.
Disclosure of Invention
In order to solve the technical problems, the invention provides the UV-cured fluorine-modified waterborne epoxy resin with strong water resistance, good weather resistance and high mechanical strength.
The invention also provides a preparation method of the UV curing fluorine modified waterborne epoxy resin, which is simple in process and high in practicability.
The invention adopts the following technical scheme:
a preparation method of UV-cured fluorine-modified waterborne epoxy resin comprises the following steps:
synthesizing fluorine-containing prepolymer: adding 30-32 parts by weight of epoxy resin, 0.1-0.2 part by weight of polymerization inhibitor, 0.5-0.8 part by weight of catalyst and 0.1-0.2 part by weight of antioxidant into a synthesis device, heating to 95-100 ℃, dropwise adding 10-12 parts by weight of acrylic acid and 30-60 parts by weight of fluorine-containing carboxylic acid, heating to 110 ℃ and reacting for 3 hours until the acid value AV is less than 5, thus obtaining fluorine-containing prepolymer;
synthesizing fluorine modified water-based epoxy resin: adding 35-38 parts by weight of fluorine-containing prepolymer into reaction equipment, stirring at 80+/-2 ℃, adding 5-10 parts by weight of anhydride, stirring at 95-100 ℃ for 3h, adding 5-8 parts by weight of triethylamine, stirring for 30min, adding 40-60 parts by weight of deionized water, and stirring at 50 ℃ for 1h to obtain fluorine-modified waterborne epoxy resin.
The technical scheme is further improved, wherein the synthetic structural formula of the fluorine-containing prepolymer is as follows:
the technical scheme is further improved, wherein the synthetic structural formula of the fluorine modified waterborne epoxy resin is as follows:
the technical scheme is further improved in that the solid content of the fluorine-modified waterborne epoxy resin is 50%, and the fluorine-modified waterborne epoxy resin is milky white liquid.
The technical scheme is further improved in that the epoxy resin is one of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin and epoxy group-containing resin.
The technical scheme is further improved that the fluorine-containing carboxylic acid is one of tridecanfluoroheptanoic acid, undecanoic acid, trifluoroacetic acid, pentafluoropropionic acid and heptafluorobutyric acid.
The technical scheme is further improved in that the anhydride is one of tetrahydrophthalic anhydride, maleic anhydride, phthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride and succinic anhydride.
The technical scheme is further improved in that the catalyst is one or a combination of more than two of triphenylphosphine, triphenylantimony, triethylamine, 2-methylaminopyridine and tetra-n-butyl ammonium bromide.
The technical proposal is further improved that the polymerization inhibitor is one or more than two of hydroquinone, p-methoxyphenol, p-hydroxyanisole, 2, 5-dimethyl hydroquinone, 1, 4-naphthalene diphenol or corresponding quinone thereof; the antioxidant is one or more than two of 2, 6-di-tert-butyl-p-cresol, 1, 3-tri (2-methyl-4 hydroxy-5-tert-butylphenyl) butane and 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
The UV-cured fluorine-modified waterborne epoxy resin is prepared by the preparation method.
The beneficial effects of the invention are as follows:
the invention provides high hardness, excellent chemical resistance and high reactivity through the epoxy resin; the grafted fluorine-containing monomer can improve the weather resistance, mechanical strength and water resistance of the epoxy resin after film formation; the anhydride substance can provide hydrophilic groups to improve the hydrophilicity of the resin, so that the resin becomes aqueous resin; the catalyst is used for catalyzing the epoxy ring-opening reaction, and the polymerization inhibitor is used for preventing the explosion polymerization in the resin synthesis process; the antioxidant has the function of increasing the stability of the resin in the storage process; triethylamine is used as a neutralizing agent to neutralize the resin and increase the hydrophilicity of the resin.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the present invention.
A preparation method of UV-cured fluorine-modified waterborne epoxy resin comprises the following steps:
synthesizing fluorine-containing prepolymer: adding 30-32 parts by weight of epoxy resin, 0.1-0.2 part by weight of polymerization inhibitor, 0.5-0.8 part by weight of catalyst and 0.1-0.2 part by weight of antioxidant into a synthesis device, heating to 95-100 ℃, dropwise adding 10-12 parts by weight of acrylic acid and 30-60 parts by weight of fluorine-containing carboxylic acid, heating to 110 ℃ and reacting for 3 hours until the acid value AV is less than 5, thus obtaining fluorine-containing prepolymer;
synthesizing fluorine modified water-based epoxy resin: adding 35-38 parts by weight of fluorine-containing prepolymer into reaction equipment, stirring at 80+/-2 ℃, adding 5-10 parts by weight of anhydride, stirring at 95-100 ℃ for 3h, adding 5-8 parts by weight of triethylamine, stirring for 30min, adding 40-60 parts by weight of deionized water, and stirring at 50 ℃ for 1h to obtain fluorine-modified waterborne epoxy resin.
Further, the synthetic structural formula of the fluorine-containing prepolymer is as follows:
further, the synthetic structural formula of the fluorine modified waterborne epoxy resin is as follows:
further, the fluorine-modified aqueous epoxy resin has a solid content of 50%, and is a milky white liquid.
Further, the epoxy resin is one of bisphenol A epoxy resin, bisphenol F epoxy resin, phenolic epoxy resin and epoxy group-containing resin.
Further, the fluorine-containing carboxylic acid is one of tridecanfluoroheptanoic acid, undecanoic acid, trifluoroacetic acid, pentafluoropropionic acid and heptafluorobutyric acid.
Further, the anhydride is one of tetrahydrophthalic anhydride, maleic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and succinic anhydride.
Further, the catalyst is one or the combination of more than two of triphenylphosphine, triphenylantimony, triethylamine, 2-methylaminopyridine and tetra-n-butyl ammonium bromide.
Further, the polymerization inhibitor is one or more of hydroquinone, p-methoxyphenol, p-hydroxyanisole, 2, 5-dimethyl hydroquinone, 1, 4-naphthalene diphenol or corresponding quinone thereof; the antioxidant is one or more than two of 2, 6-di-tert-butyl-p-cresol, 1, 3-tri (2-methyl-4 hydroxy-5-tert-butylphenyl) butane and 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
The UV-cured fluorine-modified waterborne epoxy resin is prepared by the preparation method.
Example 1
Adding 30.83g of epoxy resin, 0.15g of para-hydroxyanisole, 0.15g of 2, 6-di-tert-butyl-p-cresol and 0.5g of triphenylphosphine into a flask, heating to 95 ℃, stirring, dropwise adding 5.66g of acrylic acid for 0.5h, dropwise adding 57.23g of tridecanfluoroheptanoic acid for 1h after the acrylic acid is added, heating to 110 ℃ after the adding is finished, stirring for 3h, measuring the acid value <5, and discharging;
36g of the prepolymer is taken and placed in a flask, 8.58g of tetrahydrophthalic anhydride is added, stirring is carried out for 3 hours at 95 ℃, 5.71g of triethylamine is added, stirring is carried out for 30 minutes, 50.29g of deionized water is added, stirring is carried out for 1 hour at 50 ℃, and the fluorine modified aqueous epoxy resin of milky white liquid with 50% of solid content is obtained.
Example 2
30.83g of epoxy resin, 0.15g of para-hydroxyanisole, 0.15g of 2, 6-di-tert-butyl-p-cresol and 0.5g of triphenylphosphine are put into a flask, the temperature is raised to 95 ℃ and stirred, 5.66g of acrylic acid is dropwise added for 0.5h, 49.37g of undecanoic acid is dropwise added for 1h after the acrylic acid is completely added, the temperature is raised to 110 ℃ and stirred for 3h after the acrylic acid is completely added, the acid value of <5 is measured, and the material is discharged.
33.18g of the prepolymer was placed in a flask, 5.53g of maleic anhydride was added, stirred at 95℃for 3 hours, 5.71g of triethylamine was added, stirred for 30 minutes, 44.42g of deionized water was added, and stirred at 50℃for 1 hour, to obtain a milky white liquid fluorine-modified waterborne epoxy resin having a solid content of 50%.
Example 3
30.83g of epoxy resin, 0.15g of para-hydroxyanisole, 0.15g of 2, 6-di-tert-butyl-p-cresol and 0.5g of triphenylphosphine are put into a flask, the temperature is raised to 95 ℃ and stirred, 5.66g of acrylic acid is dropwise added for 0.5h, 41.51g of undecanoic acid is dropwise added for 1h after the acrylic acid is completely added, the temperature is raised to 110 ℃ and stirred for 3h after the acrylic acid is completely added, the acid value of <5 is measured, and the material is discharged.
30.37g of the prepolymer is taken and put into a flask, 5.53g of maleic anhydride is added, stirring is carried out for 3 hours at 95 ℃, 5.71g of triethylamine is added, stirring is carried out for 30 minutes, 41.61g of deionized water is added, stirring is carried out for 1 hour at 50 ℃, and the fluorine modified aqueous epoxy resin of milky white liquid with the solid content of 50% is obtained.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. The preparation method of the UV-cured fluorine-modified waterborne epoxy resin is characterized by comprising the following steps of:
synthesizing fluorine-containing prepolymer: adding 30-32 parts by weight of epoxy resin, 0.1-0.2 part by weight of polymerization inhibitor, 0.5-0.8 part by weight of catalyst and 0.1-0.2 part by weight of antioxidant into a synthesis device, heating to 95-100 ℃, dropwise adding 10-12 parts by weight of acrylic acid and 30-60 parts by weight of fluorine-containing carboxylic acid, heating to 110 ℃ and reacting for 3 hours until the acid value AV is less than 5, thus obtaining fluorine-containing prepolymer;
synthesizing fluorine modified water-based epoxy resin: adding 35-38 parts by weight of fluorine-containing prepolymer into reaction equipment, stirring at 80+/-2 ℃, adding 5-10 parts by weight of anhydride, stirring at 95-100 ℃ for 3h, adding 5-8 parts by weight of triethylamine, stirring for 30min, adding 40-60 parts by weight of deionized water, and stirring at 50 ℃ for 1h to obtain fluorine-modified waterborne epoxy resin.
2. The method for producing a UV-curable fluorine-modified aqueous epoxy resin according to claim 1, wherein the fluorine-modified aqueous epoxy resin has a solid content of 50%, and the fluorine-modified aqueous epoxy resin is a milky white liquid.
3. The method for preparing a UV curable fluorine modified waterborne epoxy resin according to claim 1, wherein the epoxy resin is one of bisphenol a epoxy resin, bisphenol F epoxy resin, novolac epoxy resin and epoxy group-containing resin.
4. The method for producing a UV curable fluorine modified aqueous epoxy resin according to claim 1, wherein the fluorine-containing carboxylic acid is one of tridecanfluoroheptanoic acid, undecanoic acid, trifluoroacetic acid, pentafluoropropionic acid, and heptafluorobutyric acid.
5. The method for preparing the UV-curable fluorine-modified waterborne epoxy resin according to claim 1, wherein the acid anhydride is one of tetrahydrophthalic anhydride, maleic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and succinic anhydride.
6. The method for preparing the UV-curable fluorine-modified waterborne epoxy resin according to claim 1, wherein the catalyst is one or a combination of more than two of triphenylphosphine, triphenylantimony, triethylamine, 2-methylaminopyridine and tetra-n-butylammonium bromide.
7. The method for preparing the UV-curable fluorine-modified waterborne epoxy resin according to claim 1, wherein the polymerization inhibitor is one or more of hydroquinone, p-methoxyphenol, p-hydroxyanisole, 2, 5-dimethyl hydroquinone, 1, 4-naphthalene diphenol or a corresponding quinone thereof; the antioxidant is one or more than two of 2, 6-di-tert-butyl-p-cresol, 1, 3-tri (2-methyl-4 hydroxy-5-tert-butylphenyl) butane and 1,3, 5-trimethyl-2, 4, 6-tri (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene.
8. A UV-curable fluorine-modified waterborne epoxy resin, characterized in that the UV-curable fluorine-modified waterborne epoxy resin is produced using the production method according to any one of claims 1 to 7.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898567A (en) * | 2012-10-23 | 2013-01-30 | 中科院广州化学有限公司 | Fluorine-containing epoxy resin, and preparation method and application thereof |
| CN103289058A (en) * | 2013-06-06 | 2013-09-11 | 京东方科技集团股份有限公司 | Fluorine-modified epoxy acrylate resin, ultraviolet curable gloss oil and preparation method thereof, and method for coating gloss oil on substrate |
| CN104231228A (en) * | 2014-08-14 | 2014-12-24 | 广东工业大学 | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898567A (en) * | 2012-10-23 | 2013-01-30 | 中科院广州化学有限公司 | Fluorine-containing epoxy resin, and preparation method and application thereof |
| CN103289058A (en) * | 2013-06-06 | 2013-09-11 | 京东方科技集团股份有限公司 | Fluorine-modified epoxy acrylate resin, ultraviolet curable gloss oil and preparation method thereof, and method for coating gloss oil on substrate |
| CN104231228A (en) * | 2014-08-14 | 2014-12-24 | 广东工业大学 | Waterborne fluorine-containing polyurethane resin capable of being cured by UV (Ultraviolet) and preparation method of waterborne fluorine-containing polyurethane resin |
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